EP3750693B1 - Verfahren zur herstellung eines elektrisch leitenden thermoplastischen verbundmaterials - Google Patents

Verfahren zur herstellung eines elektrisch leitenden thermoplastischen verbundmaterials

Info

Publication number
EP3750693B1
EP3750693B1 EP20179848.5A EP20179848A EP3750693B1 EP 3750693 B1 EP3750693 B1 EP 3750693B1 EP 20179848 A EP20179848 A EP 20179848A EP 3750693 B1 EP3750693 B1 EP 3750693B1
Authority
EP
European Patent Office
Prior art keywords
composite material
manufacturing
thermoplastic
electrically conductive
hours
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP20179848.5A
Other languages
English (en)
French (fr)
Other versions
EP3750693A1 (de
Inventor
Claude Rossignol
Elise ROBERT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liebherr Aerospace Toulouse SAS
Original Assignee
Liebherr Aerospace Toulouse SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Liebherr Aerospace Toulouse SAS filed Critical Liebherr Aerospace Toulouse SAS
Publication of EP3750693A1 publication Critical patent/EP3750693A1/de
Application granted granted Critical
Publication of EP3750693B1 publication Critical patent/EP3750693B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2307/00—Use of elements other than metals as reinforcement
    • B29K2307/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0005—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3076—Aircrafts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • B64C2001/0054—Fuselage structures substantially made from particular materials
    • B64C2001/0072—Fuselage structures substantially made from particular materials from composite materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/40—Weight reduction

Definitions

  • the invention relates to a method for manufacturing a thermoplastic composite material having electrically conductive properties.
  • the invention also relates to equipment for an aerial vehicle comprising an electrically conductive thermoplastic composite material obtained from said manufacturing method.
  • thermoplastic composite materials are increasingly common in the aeronautics field because they offer many advantages over metal alloys.
  • a thermoplastic composite material is, for example, composed of a thermoplastic matrix formed by polyaryl ether ketone (PAEK), a family of semi-crystalline plastics capable of withstanding high temperatures while maintaining very high strength.
  • PAEK polyaryl ether ketone
  • the interest of these thermoplastic composite materials lies in the weight saving, but also in better resistance to fatigue and the absence of corrosion.
  • thermoplastic matrix is combined with reinforcements, mainly carbon fibers in the aeronautics field for weight reasons, and thus forms the composite thermoplastic material.
  • Thermoplastic composites are often shaped by injection. The latter is widely used because it allows for high productivity. It is well known that a thermoplastic material formed by a PAEK matrix and carbon fibers is not an electrical conductor.
  • thermoplastic composite material conductive
  • carbon nanotubes have excellent thermal, mechanical and electrical properties.
  • adding a certain amount of carbon nanotubes into a thermoplastic matrix can improve the electrical conductivity of a thermoplastic material.
  • integrating carbon nanotubes into a thermoplastic matrix is a complex and expensive process. Indeed, during an injection process to design the composite material, it is difficult to homogeneously disperse the carbon nanotubes within the thermoplastic matrix.
  • the carbon nanotube integration step can be difficult since the dispersion of the carbon nanotubes is dependent on the type of matrix used, the nature of the carbon nanotubes and the viscosity of the matrix.
  • the viscosity of the mixture increases, which complicates the process of obtaining a thermoplastic material by injection.
  • the electrical percolation threshold corresponding to a critical concentration of conductive particles allowing an increase in electrical conductivity, is strongly dependent on the dispersion of carbon nanotubes in the matrix.
  • the document US2017154703A1 discloses, according to its abstract, a method for preparing an electrically conductive composite film comprising at least one thermoplastic polymer resin and electrically conductive particles selected from graphene, carbon nanotubes, carbon nanofibers, and mixtures thereof and filiform metal nanoparticles; a method for preparing an electrically conductive laminated composite structure comprising such an electrically conductive composite film.
  • the invention aims to remedy the drawbacks of the prior art by developing a process making it possible to obtain thermoplastic composite materials which have significantly improved electrical conductivity.
  • the invention aims to provide a method for manufacturing an electrically conductive thermoplastic composite material according to claim 1.
  • the invention aims in particular to provide a simple, rapid and efficient manufacturing method for a thermoplastic composite material as an electrical conductor.
  • the invention also aims to provide an electrically conductive thermoplastic composite material obtained from the manufacturing method according to the invention intended to form equipment for a transport vehicle according to claim 6.
  • the invention also aims to provide equipment for an aerial vehicle comprising an electrically conductive thermoplastic material obtained from the method according to the invention, according to claim 9.
  • the invention relates to a method for manufacturing an electrically conductive composite material according to claim 1.
  • a composite material is a thermoplastic composite material, also called a thermoplastic composite or thermoplastic material, which is thermostable and comprises a matrix made of a high-performance thermoplastic polymer formed by aromatic nuclei.
  • Thermoplastic polymers are rigid materials that are resistant to relatively high temperatures (up to 250°C to 300°C depending on the thermoplastic materials). They are also considered insulating materials with low electrical conductivity values (between 10 -20 Siemens/meter (S/m) and 10 -10 S/m).
  • Electrical conductivity describes the electrical properties of conductive materials and refers to the material's ability to conduct electric current.
  • a conductive material means a material capable of at least discharging static electricity.
  • Such a conductive material may, for example, have an electrical conductivity greater than or equal to 10 S/m.
  • the composite material according to the invention is formed by a thermoplastic matrix comprising a polymer and short carbon fibers, thus making it possible to very significantly improve the temperature resistance of the polymer matrix.
  • the presence of carbon fibers makes it possible to maintain the mechanical properties of the thermoplastic matrix, which can be used for temperatures up to 300°C.
  • Short carbon fibers are understood to mean particularly fine carbon fibers which have a diameter of the order of one to ten micrometers and a length of between 10 and 500 micrometers and which are composed almost exclusively of carbon atoms.
  • a composite material according to the invention comprises a thermoplastic matrix formed from a thermoplastic polymer, short carbon fibers and being free of carbon nanotubes.
  • Carbon nanotubes are understood to mean graphite sheets formed from carbon atoms arranged in a hexagonal network and whose diameter is of the order of a nanometer and whose length can reach several micrometers.
  • the manufacturing method according to the invention makes it possible to obtain, unexpectedly, an electrically conductive composite material and more particularly having an electrical conductivity greater than that of a composite material comprising carbon nanotubes.
  • Said composite material obtained by the manufacturing method according to the invention has an electrical conductivity greater than 10 2 S/m.
  • said method has the advantage of being easier to implement since it is not necessary to functionalize a thermoplastic composite material by adding carbon nanotubes for it to become an electrical conductor.
  • the absence of carbon nanotubes also facilitates the manufacturing method according to the invention since the constraints of integrating carbon nanotubes into the thermoplastic matrix do not occur.
  • the manufacturing method according to the invention makes it possible to improve the electrical conductivity of a thermoplastic material without carbon nanotubes.
  • the removal of carbon nanotubes makes it easier to obtain a thermoplastic material. More precisely, it eliminates viscosity constraints and the constraints relating to the step of dispersing carbon nanotubes homogeneously in a thermoplastic matrix.
  • Said manufacturing method comprises a step of obtaining said composite material.
  • the obtaining step consists of having (or manufacturing) a thermoplastic composite material comprising a thermoplastic matrix, short carbon fibers and being free of carbon nanotubes.
  • said manufacturing method comprises a furnace preheating step of preheating a furnace that is used during the heat treatment.
  • the preheating is carried out to a predetermined target temperature.
  • the predetermined target temperature is the fixed temperature at which the furnace is located when it has been preheated and it is maintained throughout the duration of the heat treatment.
  • said manufacturing method comprises a step of inserting said composite material into said preheated oven, once the target temperature has been reached.
  • said manufacturing method comprises a step of heating said composite material in said oven to the predetermined target temperature, kept constant for a predetermined duration.
  • the term "constant" means that the target temperature is reached and remains substantially the same throughout the duration of a heat treatment with a variation of plus or minus 10°C.
  • the steps of inserting and heating said composite material form the heat treatment which consists of carrying out aging on said thermoplastic material. Aging allows said thermoplastic material to undergo a chemical modification, particularly at the level of the matrix organization.
  • the heat treatment acts directly on the macromolecular chains by reducing their movements. This consequently leads to a change in crystalline morphology which results in an increase in the crystallinity rate and therefore in crosslinking.
  • the favorable change in the crystallinity rate thus promotes the electrical conductivity of the thermoplastic material treated by said heat treatment and in particular by the heating step.
  • said step of obtaining said composite material consists of mixing short carbon fibers in said thermoplastic matrix to form granules, then assembling said granules to form said composite material.
  • said obtaining step comprises a first step of mixing the carbon fibers and the thermoplastic matrix to form granules and a second step of assembling the granules which consists of assembling the granules together to form said composite material in the form of a test piece or a part.
  • said granules are assembled to form said composite material by means of a high-pressure injection molding process.
  • said composite material is obtained by means of a high-pressure injection molding process.
  • the high-pressure injection molding process allows in particular automation of the process and makes it possible to have a thermoplastic material having interesting properties such as mechanical resistance, corrosion resistance, and tensile strength.
  • thermoplastic material obtained during the production step may be formed using other methods known to those skilled in the art.
  • said mixing step is replaced by a step of acquiring the commercial material PEEK 90HMF40 of the VICTREX TM brand in the form of granules, for example.
  • said composite material is obtained from granules of a material marketed under the name PEEK 90HMF40 of the VICTREX TM brand.
  • This material comprises a thermoplastic matrix formed of a polyether ether ketone polymer, into which approximately 40% of short carbon fibers are integrated.
  • Said commercial material is easily accessible because it is simple to obtain the material in the form of granules. Also, the mixing step is replaced by the purchase of granules ready to be assembled to form the composite material which is processed by said manufacturing method according to the invention in order to obtain the electrically conductive thermoplastic composite material according to the invention.
  • this commercial material makes it possible to avoid the said mixing step by replacing it with the purchase of the material in the form of granules.
  • said thermoplastic matrix is a polyketone, preferably polyether ether ketone.
  • said thermoplastic matrix is a polyketone which is part of the family of high-performance thermoplastic polymers. More specifically, said polymer is a polyaryl ether ketone (PAEK) and mainly polyether ether ketone (PEEK) or polyether ketone ketone (PEKK).
  • PAEK polyaryl ether ketone
  • PEEK polyether ether ketone
  • PEKK polyether ketone ketone
  • PEEK has many advantages, including its resilience, mechanical modulus, thermal resistance and chemical inertness.
  • PEEK is a high-performance material that can withstand high temperatures (around 200°C to 300°C).
  • said composite material comprises a mass content of short carbon fibers of between 20 and 45%.
  • the short carbon fibers provide improved thermal and mechanical resistance to said composite material as well as dimensional stability. Also, during the heating step of said composite material, the short carbon fibers contribute to increasing the crosslinking of the thermoplastic matrix and thus allow an improvement in the electrical conductivity when said thermoplastic material is heated for a certain duration at a target temperature.
  • said predetermined duration of said step of heating said composite material varies as a function of said predetermined target temperature.
  • the predetermined duration of said heating step of said composite material will be all the longer the lower the predetermined target temperature.
  • the duration of heat treatment can be adapted according to the electrical conductivity to be achieved for a thermoplastic material. Indeed, when said oven reaches a predetermined target temperature and the composite material is introduced into said oven; the longer the duration of the heating step of said material, the more the conductivity of the thermoplastic material is improved.
  • the temperature can also be adjusted according to the duration of the heat treatment. Indeed, the higher the oven temperature, the shorter the duration of the heating stage of the heat treatment. The duration of the heating stage therefore varies according to the temperature and vice versa.
  • said predetermined target temperature is between 200°C and 300°C ⁇ 10°C.
  • Said composite material undergoes a heating step for a predetermined duration in a preheated oven at a predetermined fixed temperature. Once this temperature is reached during the preheating step of said oven, the predetermined temperature is kept fixed and constant during the heating step of said composite material. In other words, the temperature is said to be constant when it is generally maintained at the target temperature and a deviation of plus or minus 10°C is allowed during the heating step of said composite material.
  • said predetermined duration of said heating stage is between two hours and 30 hours.
  • Said predetermined duration of the heating step of said composite material corresponds to the duration during which said thermoplastic composite material is heated in said oven to a target temperature which is constant.
  • the invention also relates to an electrically conductive composite material obtained from said manufacturing method according to the invention.
  • said electrically conductive composite material obtained from said manufacturing process has an electrical conductivity of between 10 1 Siemens/meter and 10 3 Siemens/meter.
  • said composite material comprising short carbon fibers in the absence of carbon nanotubes and manufactured by the process according to the invention therefore has a high electrical conductivity of the order of 50 to 200 Siemens/meter (S/m) for a treatment duration of between two hours and 30 hours.
  • Said electrically conductive composite material obtained from said manufacturing method is a self-heating material.
  • an increase in the temperature of the composite material is generated when an electric current passes through said electrically conductive composite material. Therefore, said electrically conductive composite material allows the passage of an electric current and can thus ensure the temperature maintenance or defrosting of a part formed by said composite material.
  • the invention also relates to a use of said electrically conductive composite material according to the invention, for forming parts intended to be arranged in a transport vehicle, in particular a railway vehicle or an air vehicle.
  • said composite material electrically conductive is used to maintain the temperature of said parts intended to be arranged in a transport vehicle.
  • the parts formed by said composite material are electrically conductive and can maintain a desired temperature.
  • this makes it possible to avoid conduction losses and to heat said part to increase performance.
  • a conduit formed by said electrically conductive composite material makes it possible to maintain said conduit at temperature in order to limit heat exchange.
  • the invention therefore makes it possible to obtain a temperature maintenance method which consists of using a part formed by an electrically conductive composite material and supplying this part with an electric current so as to increase the temperature of said part to allow the temperature of this part to be maintained.
  • said electrically conductive composite material is used to defrost said parts intended to be arranged in a transport vehicle.
  • the parts formed by said composite material are electrically conductive and can be defrosted when an electric current passes through them.
  • the invention therefore makes it possible to obtain a defrosting method which consists of using a part formed by an electrically conductive composite material and supplying this part with an electric current so as to increase the temperature of said part to enable it to defrost.
  • the invention also relates to equipment for an aerial vehicle, in particular a pneumatic valve body, an actuator body, a mixing chamber, a low-pressure distribution pipe, a turbine volute, an electrical box comprising said composite material according to the invention.
  • any equipment of an aerial vehicle formed by a composite material can be formed by a composite material according to the invention.
  • the equipment formed from a composite material may be arranged either in an air system such as, for example, turbines or condensers, or in another system outside the air system such as for example a leading edge slat on a wing or wings of a turboprop aircraft.
  • equipment formed from a composite material can be heated when an electric current passes through it in order to be maintained at temperature or defrosted.
  • the equipment formed by said composite material is lighter than the equipment formed by an aluminum alloy, which consequently makes it possible to lighten the aerial vehicle in which it is arranged.
  • thermoplastic material comprising only a thermoplastic matrix and short carbon fibers, and being free of carbon nanotubes.
  • step 10 of obtaining the composite material comprises a first compounding step 11 allowing the mixing of the components (short carbon fibers and PEEK polymer) to obtain granules of composite material.
  • the mixing of the components is done with softening of the PEEK polymer.
  • thermoplastic materials used in the form of "compounds” also called composites or plastic granules.
  • the PEEK thermoplastic matrix and carbon fibers are mixed to obtain the composite material, in the form of granules.
  • the first mixing step 11 can also be replaced by purchasing a commercially available composite material in the form of granules.
  • the granules are then assembled by being melted, extruded or molded to manufacture parts of thermoplastic material.
  • the granules can be assembled to form plates using the hot plate press method, better known as "Hot plate press”.
  • the plates obtained can then be shaped as needed to form a part, particularly aircraft equipment such as a casing, for example.
  • the pellets may be injection molded to form parts of thermoplastic material.
  • the second step 12 is carried out according to this latter embodiment which consists of assembling granules of composite material obtained during the mixing step 11 to form the test pieces of thermoplastic composite materials. by injection molding.
  • a test piece is a material in the form of standardized manufacturing parts that are intended to be used to study the behavior of a material.
  • Injection molding also called plastic injection, consists of manufacturing parts from thermoplastic material in powder or granule form using plastic injection presses.
  • the thermoplastic material in granule or powder form is introduced into a hopper to feed a plasticizing screw contained in a heated barrel.
  • a first plasticizing phase 13 allows the material to pass from a solid state to a molten state by the heat provided by the resistances and the shear induced by the rotation of the screw.
  • Then follows the injection phase 14, which consists of pushing the material through the screw into a hot mold.
  • the compacting phase 15 allows the cavity to be maintained under pressure, which fills with thermoplastic material as the part cools and shrinks.
  • Step 20 of preheating the furnace consists of preheating the furnace into which the composite materials obtained in step 10 are introduced.
  • the furnace is configured to be able to reach the predetermined target temperature, i.e. the furnace temperature to which the composite materials can be heated.
  • Preheating the furnace makes it possible to heat the furnace until it reaches, in this embodiment, a temperature of 250°C with an acceptable variation of ⁇ 10°C.
  • the furnace temperature is measured using a temperature probe or a temperature recorder integrated into the furnace.
  • the preheating time to reach the temperature of 250°C depends on the furnace used and its performance.
  • Step 31 of inserting the composite material consists of inserting the thermoplastic composite material test pieces obtained in step 10 into the preheated oven which has reached the target temperature which, according to this embodiment, is 250°C.
  • Heating step 32 heats the specimens inserted into the furnace to 250°C for a predetermined time.
  • heated test tubes were used each for durations of 1 hour, 3 hours, 5 hours, 16 hours, 18 hours, 24 hours and 25 hours.
  • Heating of the specimens is carried out by maintaining the furnace at the target temperature.
  • step 40 of cooling the electrically conductive composite material allowed the specimens that had undergone the heat treatment to cool.
  • the specimens were cooled in ambient air for 30 minutes.
  • a succession of heating steps may be provided.
  • Each heating step is characterized by a predetermined temperature and duration distinct from the previous heating step.
  • a first heating step may be provided in an oven at 250°C for 5 hours, followed by a second heating step in an oven at 190°C for 2 hours.
  • FIG. 2 illustrates graphs representing the evolution of the electrical conductivity as a function of the duration of a heat treatment 30 comprising a step 31 of insertion and a step 32 of heating the material.
  • the materials analyzed at the figure 2 are in the form of test pieces which have undergone the aging process according to heat treatment 30 of the manufacturing process.
  • Four thermoplastic materials, each with a distinct composition, are analyzed before (0 hours of heat treatment) and after heat treatment (1 hour, 3 hours, 5 hours, 16 hours, 18 hours, 24 hours and 25 hours depending on the materials).
  • the different materials tested and presented in the figure 2 all include a polyether ether ketone (PEEK) base.
  • PEEK polyether ether ketone
  • PEEK 90HMF40 material is a polymer known under the trade name of the product sold by VICTREX TM comprising a PEEK polymer reinforced with short carbon fibers at a rate of 40%.
  • PEEK 90P + 4%CNT material is a virgin PEEK polymer to which 4% carbon nanotubes have been integrated into the matrix.
  • PEEK 90P + 6.67%CNT material is a virgin PEEK polymer to which 6.67% carbon nanotubes have been integrated into the matrix.
  • PEEK 90P + 4%CNT + 30%CCF material is a virgin PEEK polymer to which 4% carbon nanotubes have been integrated into the matrix comprising 30% short carbon fibers.
  • the 90HMF40 material specimens were obtained from commercially purchased granules. Subsequently, the granules underwent assembly step 12 according to the method of figure 1 to form the test pieces.
  • the materials are in the form of test pieces with the following dimensions: 80 millimeters (mm) in length and 10 mm in width.
  • the test pieces formed by the 90HMF40 material have a thickness of 2 mm and the test pieces formed by the other materials have a thickness of 3 mm.
  • Test specimens of each material described above were introduced into a preheated furnace at a temperature of 250°C and then heated for 1 hour, 3 hours, 5 hours, 16 hours, 18 hours, 24 hours and 25 hours (depending on the materials) in the furnace at a constant temperature of 250°C.
  • the oven temperature is kept constant during the heating stage of the composite material specimens and can be checked using a temperature probe or a temperature recorder integrated into the oven.
  • the measurement of electrical conductivity is carried out on all the test pieces having undergone the heat treatment and consequently the heating step for distinct durations (1 hour, 3 hours, 5 hours, 16 hours, 18 hours, 24 hours and 25 hours). This makes it possible to establish a curve showing the evolution of electrical conductivity according to the duration of the heating step.
  • Electrical conductivity is measured in Siemens per meter (S/m) using electrical tests carried out, for example, with a Keithley 6517B ohmmeter, at an input voltage of less than 5V on test pieces. Each end of the test pieces is coated with silver paint to allow conductivity measurement. These electrical tests are carried out at room temperature using low electrical current values (in the order of mA) to avoid heating of the test pieces.
  • the graphs of the figure 2 highlight a general trend of significant increase in electrical conductivity when a material has been subjected to the aging process and in particular to the heating stage.
  • the heating step of the heat treatment gradually makes the composite material electrically conductive.
  • the composite material is not treated by heating, it is not electrically conductive. Heating will make a thermoplastic material electrically conductive.
  • the longer the material is heated the more the electrical conductivity increases. This result is observed for all PEEK materials, whether or not they contain carbon nanotubes.
  • the electrical conductivity of the PEEK 90HMF40 material treated for 25 hours is 140 S/m compared to 110 S/m for the PEEK 90P + 4%CNT + 30%CCF material treated for 25 hours. It can be seen that a material without nanotubes and having undergone heat treatment has sufficient electrical conductivity, i.e. a conductivity that at least allows the static electricity of the material to be discharged.
  • the orientation of the carbon fibers influences the electrical conductivity when analyzed along the 0°, 45° or 90° direction in the fiber direction.
  • the influence of the fiber orientation is negligible compared to the effects of the applied heat treatment.
  • the electrical conductivity is very low and the heat treatment has no effect when analyzed with the orientation along the plate thickness, for all the specimens of the four materials, heated for different durations. This confirms that the electrical conductivity in the thermoplastic material is allowed through the carbon fibers and therefore occurs in the fiber direction.
  • the presence of carbon nanotubes does not lead to a significant increase in electrical conductivity.
  • the major interest of this invention lies in the fact of using a material already known and qualified by certain players in the aeronautics industry, which through heat treatment achieves sufficient conductivity values, that is to say allowing at least the discharge of static electricity.
  • the manufacture of parts with carbon nanotubes which is difficult and expensive, and which requires the qualification of a new material for aeronautics, is not necessary.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Aviation & Aerospace Engineering (AREA)
  • Composite Materials (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Textile Engineering (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Claims (9)

  1. Verfahren zur Herstellung eines elektrisch leitfähigen Verbundmaterials, wobei das Verfahren mindestens die Schritte umfasst:
    - einen Schritt (10) des Erhaltens des Verbundmaterials, das eine thermoplastische Matrix und kurze Kohlenstofffasern umfasst und frei von Kohlenstoffnanoröhren ist, worin das Verbundmaterial einen Massengehalt an kurzen Kohlenstofffasern zwischen 20 und 45% umfasst und die kurzen Kohlenstofffasern einen Durchmesser im Bereich von einem bis zehn Mikrometern und eine Länge zwischen 10 und 500 Mikrometern aufweisen und fast ausschließlich aus Kohlenstoffatomen bestehen,
    - einen Schritt (20) des Vorheizens eines Ofens, bis eine bestimmte Zieltemperatur erreicht ist,
    - einen Schritt (31) des Einführens des Verbundmaterials in den vorgewärmten Ofen, sobald die Zieltemperatur erreicht ist, und
    - einen Schritt (32) des Erhitzens des Verbundmaterials in dem Ofen auf die bestimmte Zieltemperatur, die für eine bestimmte Dauer zwischen 2 Stunden und 30 Stunden konstant gehalten wird, wobei die bestimmte Zieltemperatur zwischen 200°C und 300°C ± 10°C liegt.
  2. Verfahren zur Herstellung eines Verbundmaterials nach Anspruch 1, dadurch gekennzeichnet, dass der Schritt (10) zum Erhalten des Verbundmaterials das Mischen (11) von kurzen Kohlenstofffasern in der thermoplastischen Matrix zur Bildung von Granulat und das anschließende Zusammenfügen (12) des Granulats zur Bildung des Verbundmaterials umfasst.
  3. Verfahren zur Herstellung eines Verbundmaterials nach Anspruch 2, dadurch gekennzeichnet, dass das Granulat zur Bildung des Verbundmaterials durch ein Hochdruck-Spritzgussverfahren zusammengefügt wird.
  4. Verfahren zur Herstellung eines Werkstoffs nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die thermoplastische Matrix ein Polyketon, vorzugsweise ein Polyetheretherketon, ist.
  5. Verfahren zur Herstellung eines Verbundmaterials nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die bestimmte Dauer des Schritts (32) des Erhitzens des Verbundmaterials in Abhängigkeit von der bestimmten Zieltemperatur variiert.
  6. Verwendung eines elektrisch leitfähigen Verbundmaterials, das durch das Herstellungsverfahren nach einem der Ansprüche 1 bis 5 erhalten wurde, zum Formen von Teilen, die in einem Transportfahrzeug, insbesondere einem Schienenfahrzeug oder einem Luftfahrzeug, angeordnet werden sollen.
  7. Verwendung nach Anspruch 6 zur Aufrechterhaltung der Temperatur der Teile, die dazu bestimmt sind, in einem Transportfahrzeug angeordnet zu werden.
  8. Verwendung nach Anspruch 6 zur Enteisung der Teile, die in einem Transportfahrzeug angeordnet werden sollen.
  9. Vorrichtung eines Luftfahrzeugs, insbesondere ein pneumatischer Ventilkörper, ein Aktuatorkörper, eine Mischkammer, eine Niederdruckförderleitung, ein Turbinenradsatz oder ein elektrisches Gehäuse, die ein Verbundmaterial umfassen, das durch das Verfahren zur Herstellung nach einem der Ansprüche 1 bis 5 erhalten wurde.
EP20179848.5A 2019-06-14 2020-06-12 Verfahren zur herstellung eines elektrisch leitenden thermoplastischen verbundmaterials Active EP3750693B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1906414A FR3097160B1 (fr) 2019-06-14 2019-06-14 Procédé de fabrication d’un materiau composite thermoplastique électriquement conducteur

Publications (2)

Publication Number Publication Date
EP3750693A1 EP3750693A1 (de) 2020-12-16
EP3750693B1 true EP3750693B1 (de) 2025-07-30

Family

ID=68072721

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20179848.5A Active EP3750693B1 (de) 2019-06-14 2020-06-12 Verfahren zur herstellung eines elektrisch leitenden thermoplastischen verbundmaterials

Country Status (3)

Country Link
US (1) US11557406B2 (de)
EP (1) EP3750693B1 (de)
FR (1) FR3097160B1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20250154319A1 (en) 2023-11-15 2025-05-15 Eaton Intelligent Power Limited Thermally conductive and electrically insulating high temperature polymers

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060235135A1 (en) * 2003-04-24 2006-10-19 Showa Denko K.K. Resin crystallization promoter and resin composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008006166A1 (en) * 2006-07-13 2008-01-17 Orica Explosives Technology Pty Ltd Electrical conductive element
JP5958347B2 (ja) * 2011-11-29 2016-07-27 東レ株式会社 炭素繊維強化熱可塑性樹脂組成物、そのペレットおよび成形品
GB201206885D0 (en) * 2012-04-19 2012-06-06 Cytec Tech Corp Composite materials
GB201214181D0 (en) 2012-08-08 2012-09-19 Innovative Carbon Ltd Conductive polymeric materials and uses thereof
FR3023746B1 (fr) * 2014-07-21 2016-07-29 Univ Paul Sabatier - Toulouse Iii Procede de preparation d'une structure composite stratifiee electriquement conductrice

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060235135A1 (en) * 2003-04-24 2006-10-19 Showa Denko K.K. Resin crystallization promoter and resin composition

Also Published As

Publication number Publication date
FR3097160B1 (fr) 2022-08-19
EP3750693A1 (de) 2020-12-16
US20200395144A1 (en) 2020-12-17
US11557406B2 (en) 2023-01-17
FR3097160A1 (fr) 2020-12-18

Similar Documents

Publication Publication Date Title
EP2294253B1 (de) Verfahren zur herstellung leitfähiger verbundfasern, in diesem verfahren hergestellte fasern und verwendung solcher fasern
EP3105025B1 (de) Verfahren zur herstellung eines fasermaterials, das mit einem thermoplastischen polymer in einem fliessbett vorimprägniert ist
BE1024615B1 (fr) Compositions de polymeres thermiquement conducteurs contenant du noire de carbone
EP3617254A1 (de) Fasermaterial, das mit thermoplastischem polymer imprägniert ist
FR3023746A1 (fr) Procede de preparation d'une structure composite stratifiee electriquement conductrice
EP3768768B1 (de) Fasermaterial impregniert mit thermoplastischem polymer und mit einer dicke von weniger als oder gleich 100 mikrometer, und sein herstellungsverfahren
EP2081989A1 (de) Leitfähiger verbundwerkstoff mit thermoplastischem polmer und kohlenstoffnanoröhrchen
FR2992321A1 (fr) Procede de fabrication d'un materiau fibreux pre-impregne de polymere thermoplastique.
Pan et al. Dynamic oscillatory rheological properties of polystyrene/poly (methyl methacrylate) blends and their composites in the presence of carbon black
WO2013182830A2 (fr) Procédé de dévulcanisation d'un caoutchouc vulcanisé
WO2017017388A1 (fr) Procédé pour matériau fibreux pre-impregne par un polymère thermoplastique a l'aide d'un polymère a cristaux liquides
EP3750693A1 (de) Verfahren zur herstellung eines elektrisch leitenden thermoplastischen verbundmaterials
FR2982869A1 (fr) Additif a base de poudre de charbon vegetal pour matrice polymere ou similaire
FR3057873A1 (fr) Materiau composite electriquement et thermiquement conducteur
EP3853936A1 (de) Zusammensetzungen für bipolare platten und verfahren zur herstellung der besagten zusammensetzungen
FR3084008A1 (fr) Procede de soudage par induction mettant en œuvre un film polymere composite conducteur et/ou magnetique
EP3853295A1 (de) Zusammensetzungen für bipolare platten und verfahren zur herstellung dieser zusammensetzungen
CA2864211A1 (fr) Traitement anti-adherent de moules composites
FR3017818A1 (fr) Procede sans solvants pour preimpregner au moins une fibre avec un fluide a tres grande vitesse
FR2974092A1 (fr) Procede de fabrication de composants par pim, base sur l'utilisation de fibres ou fils organiques, avantageusement couplee a l'utilisation de co2 supercritique
FR2829720A1 (fr) Procede pour la mise en oeuvre par extrusion-soufflage d'un hdpe usage
Fan et al. Study on the properties of short carbon fiber/linear low-density polyethylene conductive composites prepared by spatial confining forced network assembly method
FR3104589A1 (fr) Procédé de préparation d’un matériau composite électriquement conducteur et matériau composite électriquement conducteur obtenu par un tel procédé
FR3057571A1 (fr) Materiau de repartition de champ electrique, son procede de fabrication et dispositif comprenant un tel materiau
CH719959A1 (fr) Plaque bipolaire pour pile à combustible et son procédé de fabrication.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210608

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20221201

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: B64C 1/00 20060101ALI20250122BHEP

Ipc: B29C 70/88 20060101ALI20250122BHEP

Ipc: B29C 70/12 20060101AFI20250122BHEP

INTG Intention to grant announced

Effective date: 20250205

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602020055347

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20250730

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1818506

Country of ref document: AT

Kind code of ref document: T

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251030

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251030

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250730